CN103113574A - Preparation method of nano/microstructure polyetherketone crystal - Google Patents
Preparation method of nano/microstructure polyetherketone crystal Download PDFInfo
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- CN103113574A CN103113574A CN2013100421824A CN201310042182A CN103113574A CN 103113574 A CN103113574 A CN 103113574A CN 2013100421824 A CN2013100421824 A CN 2013100421824A CN 201310042182 A CN201310042182 A CN 201310042182A CN 103113574 A CN103113574 A CN 103113574A
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Abstract
The invention relates to a preparation method of a nano/microstructure polyetherketone crystal, particularly a preparation method of a nano polyetherketone crystal, belonging to the fields of chemical engineering and fine chemical engineering. The method comprises the following steps: preparing corresponding polyetherketone crystal sample wafers with a polyetherketone crystal sample wafer preparation device at different temperatures for different constant-temperature time periods, pulverizing into particles with certain size with a special pulverizer, adding into a flooding extractor, leaching diphenyl sulfone with acetone, leaching villiaumite with water, and the like; and finally, drying to obtain the refined polyetherketone material wafer. In conclusion, the invention has the advantages of short refinement time, low energy consumption, low pure water consumption, small wastewater generation amount, energy saving and consumption reduction, is beneficial to enhancing the production capacity, and enhances the production efficiency.
Description
Technical field
The invention belongs to chemical engineering, field of fine chemical, particularly relate to a kind of preparation method of nano level polyetherketone crystallisate.
Background technology
In the middle of prior art polyetherketone synthetic be in sulfobenzide as solvent, as raw material, lower reaction makes under the condition that salt of wormwood exists with 4,4 – difluoro benzophenones and Resorcinol.After reaction finished, product, solvent, by product etc. were entrained in together, form solid mixture under normal temperature.After reaction finished, with the solvent sulfobenzide in organic solvent leaching solids mixing, water leached by product villiaumite and raw material salt of wormwood etc., and then drying obtains pure polyetherketone.In process of production, reaction product is processed, then made with extra care through special-purpose compressing tablet, cooling, disintegrating apparatus.Affect the many factors of polyether ketone refinement leaching, mainly contain following several respects: the 1) globule size of polyetherketone particle, the size of granule interior hole, specific surface area, void shape and solute distribution etc. in particle.2) solvent is kind, viscosity, activity and the spread coefficient etc. of leaching agent.3) service temperature, pressure, stirring velocity and flow of solvent state etc.4) leaching liquid and the solute absorption situation on inert component.Polyetherketone to certain production technique production, the character of its particle, operational condition, solvent classification and solute and solvent is substantially definite, improve polyether ketone refinement efficient, under original research and production specifications, study its crystal habit, the polyether ketone refinement speed of taping the latent power is the effective ways that improve its production efficiency.Early stage work study the improvement etc. of the pulverizing of polyetherketone, the leaching of different leaching liquids, different leaching technology and different process, polyether ketone refinement efficient is greatly improved.But, due to the polyetherketone Study on Crystallization Process deeply do not reach the expansion of throughput, the refining time is still long, energy consumption is larger, pure water consumption and waste water generation are too much, make treating process become the bottleneck of whole production process.For this reason, according to the nano-micro structure interface result of study to mass transfer, Heat Transfer Influence, structure for polyetherketone particle after pulverizing, in conjunction with refining principle, and polyetherketone crystallization influence factor, the further structure of research polyetherketone particle of crystallization under differing temps, expect to have better mass transfer effect, its the refining speed of taping the latent power, energy-saving and cost-reducing, enhance productivity.
During the polyetherketone crystallization, due to be with the mixture of the composition such as solvent sulfobenzide in carry out, therefore, the shape of crystallisate and the size of the hole dimension between crystallisate greatly affect refining time of polyetherketone.Because the refining initial stage is the dissolution process of surface or hole shallow-layer place solute, dissolution rate is very fast, and the refining progress in this stage is also very fast.From the leaching liquid solute concentration originally pace of change comparatively fast can prove this point.But along with going deep into for the treatment of process, sulfobenzide is immersed polyetherketone crystalline mixture surface takes down, and hole occurs, and just there is a diffusion mass transfer process in its inner solute of re-leaching, and hole is larger, more is conducive to mass transfer, and leaching speed is just faster.Simultaneously, the polyetherketone product at nano-micro structure interface is arranged, the ultrafine powder processing in the later stage has some superiority in granulation, also all can affect polyetherketone production efficiency to a certain extent.
Summary of the invention
Technical problem to be solved by this invention is: with the polyetherketone crystallisate print preparation facilities of Fig. 1, in differing temps, different constant temperature times, prepare corresponding polyetherketone crystallisate print, then use special-purpose disintegrating apparatus, it is ground into the particle of certain size, then be put in Flooding extractor, leach sulfobenzide with acetone, use water extraction villiaumite etc.Final drying, the polyetherketone material sheet after being made with extra care.
A kind of polyetherketone crystallisate preparation method of nano-micro structure is characterized in that comprising the following steps:
Step 1, employing polyetherketone crystallisate print preparing device prepare polyetherketone crystallisate print:
top tank and the upper hot-plate in lower fuel tank and lower hot-plate energising heating with polyetherketone crystallisate print preparing device, and control temperature between 130 ℃ ~ 190 ℃, adjust the distance between material compressing tablet flat board and upper hot-plate, make the thickness of material sheet reach 3mm ~ 5mm, pass into nitrogen by the import of protection gas in polyetherketone crystallisate print preparing device, prevent the oxidation in air of solvent sulfobenzide, after the preheating preparation work of polyetherketone crystallisate print preparing device is complete, polyetherketone mix products after being about to synthesize is emitted rear directly moving on on material compressing tablet flat board, shut hot-plate and remove to regulate the adjustment height turning axle by the film-making height adjustment knob, kept thermostatically heating 5 minutes ~ 20 minutes, reach predetermined constant temperature and after the time at material, taking off polyetherketone crystallisate print, to put into water cooling,
Step 3, the polyetherketone crystallisate print after pulverizing are put in Flooding extractor, at first use acetone leaching sulfobenzide wherein, and then with the remaining villiaumite of water extraction, sodium carbonate;
Step 4, the polyetherketone crystallisate after purifying through the leaching step use vacuum drying oven carry out drying.
Oxidized for preventing sulfobenzide in described step 1, be provided with protection gas outlet blocking-up air and enter in crystallizer on polyetherketone crystallisate print preparing device.
During heat-conducting oil heating in top tank and lower fuel tank, the one, cause air expansion to emit, the 2nd, cause flue gas to produce; Due to the contraction of thermal oil volume, there is air to enter top tank and lower fuel tank when thermal oil is cooling, therefore is respectively equipped with top tank oil gas vent and lower fuel tank oil gas vent on top tank and lower fuel tank.
Top tank and lower fuel tank are controlled corresponding fuel tank temperature-stable by top tank temperature probe and lower fuel tank temperature probe detected temperatures.
Top tank and lower fuel tank are opened and are closed by handle.
Prevent that the oxidized rare gas element of sulfobenzide from entering the space, material place of polyetherketone crystallisate print preparing device from the import of protection gas.
Beneficial effect: three kinds of polyetherketone crystallized products and original production are obtained product, measure mean pore size with the F-sorb2400 surveying instrument, data see Table 1.
Mean pore size data sheet after the polyetherketone product of the different methods for cooling of table 1 and temperature crystallization is refining.
| Cold 130-155 ℃ 160 ℃ of left and right 165-190 ℃ of methods for cooling speed |
| Mean pore size (um) 0.096 0.151 0.588 0.163 |
As can be seen from Table 1, pore size distribution after the polyether ketone refinement of different methods for cooling crystallizations is different, minimum when speed is cold, maximum during 160 ℃ of left and right, at this moment, its mean pore size is much larger than the mean free path 0.1um of molecule, solid materials to this kind aperture leaches, and the resistance of diffusion mass transfer mainly comes from intermolecular collision, the resistance that mass transfer is brought much smaller than molecule and hole wall collision, therefore, the refining time is bound to shorten.
Find when carrying out the polyetherketone crystallization under differing temps, too high when Tc, the solvent sulfobenzide is exposed in air or the ingress of air time oxidation can occur when longer, and the tablet surface color deepens, and temperature is higher, constant temperature time is longer, and color and luster is darker.Therefore, in operation, protection of inert gas to be arranged.
Utilize the liquid flooding extraction element that the sample of above equal in quality is made with extra care, mainly comprise acetone leaching, water extraction, then carry out drying with vacuum drying oven.What it was refining lists in respectively table 2 total time.
The thing of the polyetherketone crystallization that the different methods for cooling of table 2 obtain is made with extra care timetable used.
| Directly 160 ℃ of crystallizations of fast cold 130-155 ℃ of crystallization 165-190 ℃ crystallization of crystallization condition |
| The refining time (h) 18.8 18.2 17.4 12.6 |
Can be found out by table 2 data, the polyether ketone refinement time of 160 ℃ of lower crystallizations is 12.6h, improves 30.8% than former direct fast cold crystallization thing on purification efficiency.
Observed and the mean pore size test data of crystallisate after refining draws by scanning electron microscope (SEM) photograph, at 160 ℃ of constant temperature in the time of 5 minutes, the polyetherketone crystallisate that obtains has the nano-micro structure interface.Pore size at 0.5 micron to tens nanometers, and even structure.Just because of this nano-micro structure interface, be easy to mass transfer, heat transfer,, when refining, transfer efficiency is high.
Physical property detects: temperature change the crystallization behavior of polyetherketone, also change possibly its physical property, especially physical properties.The polyetherketone of crystallization under differing temps is carried out corresponding physical property detect, table 3 data show, by treatment of different temperature, fusing point does not change with batch material for it.
The fusing point data sheet of the polyetherketone product that the different Tcs of table 3 obtain.
| Directly 160 ℃ of crystallizations of fast cold 130-155 ℃ of crystallization 165-190 ℃ crystallization of crystallization condition |
| Molten molten index (g) 7.912 7.924 7.905 7.922 |
Material after refining coordinates the SEM scanning electron microscope, consists of with the energy spectrometer analysis element, and the polyetherketone crystallisate component of same batch 130 ℃, 160 ℃, 190 ℃ does not contain the F element in consisting of, and other chief component constituent contents are basic identical.
It is short that the present invention has the refining time in sum, and energy consumption is less, and pure water consumption and waste water generation are less, are conducive to the expansion of throughput, energy-saving and cost-reducing, enhances productivity.
Description of drawings
The present invention will be further described below in conjunction with description of drawings and embodiment.
Fig. 1 is polyetherketone crystallisate print preparing device structural representation of the present invention.
5 minutes constant temperature when Fig. 2 is 130 ℃ of the present invention, the SEM figure of section after the polyetherketone crystallisate is refining.
20 minutes constant temperature when Fig. 3 is 190 ℃ of the present invention, the SEM figure of section after the polyetherketone crystallisate is refining.
Fig. 4 is the refining rear scanning electron microscope (SEM) photograph of polyetherketone spheroidal crystal thing of the present invention.
5 minutes constant temperature when Fig. 5 is 160 ℃ of the present invention, the SEM figure after the polyetherketone crystallisate is refining.
In figure, 1-lower fuel tank, 2-protect hot-plate under gas outlet, 3-film-making height adjustment knob, 4-, 5-lower fuel tank oil gas vent, 6-material compressing tablet flat board, 7-adjustment height turning axle, the upper hot-plate of 8-, 9-top tank oil gas vent, 10-handle, 11-top tank, 12-top tank temperature probe, the import of 13-protection gas, 14-lower fuel tank temperature probe.
Embodiment
Polyetherketone crystallisate print preparing device as shown in Figure 1, in differing temps, different constant temperature times, prepare corresponding polyetherketone crystallisate print, then use special-purpose disintegrating apparatus, it is ground into the particle of certain size, then be put in Flooding extractor, leach sulfobenzide with acetone, use water extraction villiaumite etc.Final drying, the polyetherketone material sheet after being made with extra care.With the tablet of same batch of different Tcs and crystallization time, carry out electron-microscope scanning and detect, the result of various situations such as Fig. 2 are to shown in Figure 5.
Fig. 2, Fig. 3 be the polyetherketone product respectively at 130 ℃, constant temperature 5min, the SEM figure of section part after the crystallisate that 190 ℃, constant temperature 10min time obtain is refining.
By finding out in Fig. 2, Fig. 3, the polyetherketone crystallisate shape that obtains at this temperature all is approximately spherical.Just along with the rising of temperature, soaking time lengthens, the section surface after cooled product is cleaned, and its degree of roughness and hole raise with temperature and increase, but not obvious.There is projection on the surface of spheroidal crystal thing, and the said minuscule hole (see figure 4) is arranged.According to refining mass transfer theory, between geode, more large more being conducive to of hole makes with extra care, and the said minuscule hole on the geode spheroid will inevitably restrict refining speed to a certain extent.
Under 160 ℃, azeotropic 5min condition, larger variation, crystalline form such as Fig. 5 occur in the crystalline state of polyetherketone in product. and as can be seen from Figure 5, the polyetherketone crystallisate under this condition is spongy, and relative porosity factor is larger, and structure compared is even, and alternate contact surface is larger.On the mass transfer principle, easily carry out mass-and heat-transfer when refining, be conducive to improve refining speed.
With the top tank 11 of polyetherketone crystallisate film-making device polyetherketone crystallisate print preparing device, lower hot-plate 4 in lower fuel tank 1 and the 8 energising heating of upper hot-plate, and control to 160 ± 3 ℃.Adjust material compressing tablet dull and stereotyped 6 and upper hot-plate 8 spacings, make the material sheet reach pre-determined thickness.Pass into nitrogen by protection gas import 13 in polyetherketone crystallisate film-making device, prevent the oxidation in air of solvent sulfobenzide.Polyetherketone mix products after synthetic is emitted rear directly moving on on material compressing tablet flat board 6, shut upper cover hot-plate 8 and tighten film-making height adjustment knob 3 and remove to regulate adjustment height turning axle 7, guarantee constant temperature and constant temperature time.Reach predetermined constant temperature and after the time at material, taking off polyetherketone crystallisate tablet, to put into water cooling, just has the nano-micro structure of Fig. 5 in the polyetherketone crystallisate tablet that obtains.
Control different temperature, keep different constant temperature times, just can obtain the crystalline wafer of differing temps, different constant temperature times.
Claims (6)
1. the polyetherketone crystallisate preparation method of a nano-micro structure is characterized in that comprising the following steps:
Step 1, employing polyetherketone crystallisate print preparing device prepare polyetherketone crystallisate print:
top tank (11) and the upper hot-plate (8) in lower fuel tank (1) and lower hot-plate (4) energising heating with polyetherketone crystallisate print preparing device, and control temperature between 130 ℃ ~ 190 ℃, adjust the distance between material compressing tablet dull and stereotyped (6) and upper hot-plate (8), make the thickness of material sheet reach 3mm ~ 5mm, pass into nitrogen by protection gas import (13) in polyetherketone crystallisate print preparing device, prevent the oxidation in air of solvent sulfobenzide, after the preheating preparation work of polyetherketone crystallisate print preparing device is complete, polyetherketone mix products after being about to synthesize is emitted rear directly moving on on material compressing tablet dull and stereotyped (6), shut hot-plate (8) and remove to regulate adjustment height turning axle (7) by film-making height adjustment knob (3), kept thermostatically heating 5 minutes ~ 20 minutes, reach predetermined constant temperature and after the time at material, taking off polyetherketone crystallisate print, to put into water cooling,
Step 2, cooled polyetherketone crystallisate print is placed in pulverizer, it is ground into the Polygons particle with 3 ~ 5 limits that the length of side is 3mm ~ 4mm;
Step 3, the polyetherketone crystallisate print after pulverizing are put in Flooding extractor, at first use acetone leaching sulfobenzide wherein, and then with the remaining villiaumite of water extraction, sodium carbonate;
Step 4, the polyetherketone crystallisate after purifying through the leaching step use vacuum drying oven carry out drying.
2. the polyetherketone crystallisate preparation method of a kind of nano-micro structure according to claim 1; it is characterized in that: oxidized for preventing sulfobenzide in described step 1, be provided with protection gas outlet (2) blocking-up air and enter in crystallizer on polyetherketone crystallisate print preparing device.
3. the polyetherketone crystallisate preparation method of a kind of nano-micro structure according to claim 1 is characterized in that: during heat-conducting oil heating in top tank (11) and lower fuel tank (1), and the one, cause air expansion to emit, the 2nd, cause flue gas to produce; Due to the contraction of thermal oil volume, there is air to enter top tank (11) and lower fuel tank (1) when thermal oil is cooling, therefore is respectively equipped with top tank oil gas vent (9) and lower fuel tank oil gas vent (5) on top tank (11) and lower fuel tank (1).
4. the polyetherketone crystallisate preparation method of a kind of nano-micro structure according to claim 1 is characterized in that: top tank (11) and lower fuel tank (1) are by top tank temperature probe (12) and the corresponding fuel tank temperature-stable of lower fuel tank temperature probe (14) detected temperatures control.
5. the polyetherketone crystallisate preparation method of a kind of nano-micro structure according to claim 1, it is characterized in that: top tank (11) and lower fuel tank (1) are opened and are closed by handle (10).
6. the polyetherketone crystallisate preparation method of a kind of nano-micro structure according to claim 1, is characterized in that: prevent that the oxidized rare gas element of sulfobenzide from entering the space, material place of polyetherketone crystallisate print preparing device from protection gas import (13).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674541A (en) * | 2017-01-25 | 2017-05-17 | 山东凯盛新材料股份有限公司 | Preparation method of poly(ether-ketone-ketone) powder for electrostatic spraying based on thermal oxygen treatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996287A (en) * | 1988-12-13 | 1991-02-26 | E. I. Du Pont De Nemours And Company | Thermoformable polyaryletherketone sheet |
| CN102443122A (en) * | 2011-09-29 | 2012-05-09 | 长春工业大学 | Production method for refining polyetheretherketone |
| CN102601970A (en) * | 2012-03-07 | 2012-07-25 | 长春工业大学 | Novel polyether ketone melt filter device |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4996287A (en) * | 1988-12-13 | 1991-02-26 | E. I. Du Pont De Nemours And Company | Thermoformable polyaryletherketone sheet |
| CN102443122A (en) * | 2011-09-29 | 2012-05-09 | 长春工业大学 | Production method for refining polyetheretherketone |
| CN102601970A (en) * | 2012-03-07 | 2012-07-25 | 长春工业大学 | Novel polyether ketone melt filter device |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106674541A (en) * | 2017-01-25 | 2017-05-17 | 山东凯盛新材料股份有限公司 | Preparation method of poly(ether-ketone-ketone) powder for electrostatic spraying based on thermal oxygen treatment |
| CN106674541B (en) * | 2017-01-25 | 2019-03-26 | 山东凯盛新材料股份有限公司 | The preparation method of electrostatic spraying polyether ketone ketone powder based on the processing of hot oxygen |
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